Well cementing material

ABSTRACT

The present invention relates to a formulation of a high-performance foamed cement material, comprising: at least one hydraulic binder, microparticles whose grain size ranges between 0.1 and 30 μm, whose proportion ranges between 15% and 50% by mass in relation to the mass of hydraulic binder, mineral particles whose grain size ranges between 1 and 500 μm, whose proportion ranges between 10% and 35% by mass in relation to the mass of hydraulic binder, the proportion of particles being lower than the proportion of microparticles, a hydrosoluble polymer thinning agent whose proportion ranges between 0.1% and 8% by mass in relation to the mass of hydraulic binder, water whose proportion is at most 40% by mass in relation to the mass of hydraulic binder, a foaming agent whose proportion ranges between 0.1% and 10% by mass in relation to the mass of hydraulic binder.

FIELD OF THE INVENTION

The present invention relates to a slurry for cementing a well, notablya well intended for exploration or development of undergroundreservoirs, such as hydrocarbon or geothermal reservoirs. The inventionprovides new cementing material formulations having simultaneously lowdensities, high mechanical properties and a low permeability.

BACKGROUND OF THE INVENTION

Hydrocarbon development well cementing is a complex operation withmultiple goals: mechanically secure the casing strings in the geologicformation, isolate a producing layer from adjacent layers, protect thestrings against the corrosion due to the fluids contained in the layerscrossed through. The cement sheaths therefore have to provide goodmechanical strengths and low permeability to the fluids and to the gascontained in the formations drilled.

Under certain geothermal or hydrocarbon reservoir developmentconditions, it is essential to have cementing materials with both lowdensities and excellent physical properties (mechanical strength andpermeability). These two conditions are difficult to combine withconventional cementing materials. It is well-known since Feret'sresearch work that the mechanical strength varies conversely to theporosity. Feret notably showed that the compressive strength Rc wasexpressed as follows:${R_{c}(t)} = {{K(t)}\left( \frac{c}{c + e + v} \right)^{2}}$where c, e and v are the volumes of cement, water and air respectively,and K(t) a kinetic function.

In order to lighten cementing slurries, it is common practice toincrease either the amount of water or the amount of air (using hollowballs or by entraining intentionally a large amount of air so as to forma cement foam). According to the above formula, these two means lead toa mechanical strength degradation and, simultaneously, to a greatincrease in the permeability of the hardened material.

When the formations drilled are fragile and unconsolidated, it isimpossible to carry out operations with a dense cement slurry for fearof exceeding the fracture pressure of the formations. This problem isnotably encountered when cementing the casings of offshore wells orwells drilled in mature fields.

To cement wells crossing fragile formations, i.e. with a low fracturegradient, it is well-known to significantly lighten the slurry by addinggas. This gas can be introduced by means of hollow ceramic or glassmicrospheres. This technique is notably described in documents U.S. Pat.No. 3,804,058 and U.S. Pat. No. 4,252,193. The gas can also beintroduced into the slurry by creating a foam by means of foaming agentsadded to this slurry. This technique is notably described in documentsU.S. Pat. No. 5,806,594 and U.S. Pat. No. 5,484,019.

Cements lightened by means of hollow balls have certain drawbacks. Onedrawback is the destruction of the balls under the effect of thehydrostatic pressure. This destruction translates into a densityincrease while pumping the slurry: the fracture pressure can thus bereached. Another drawback of hollow glass balls comes from thedestruction, in the hardened cement, of the walls of the balls as aresult of pozzolanic reactions. This destruction translates into anincrease in the permeability of the cement matrix.

Common formulations of a foamed cement slurry for cementing wellscomprise a proportion of water ranging between 40% and 60% by weight ofcement. This high water amount, necessary to lower the cement slurrydensities and to optimize the rheology, generates a high porosity whichtranslates into poor properties of the cement sheath in terms ofpermeability, mechanical strength, cracking and durability.

The problem now consists in formulating a pumpable hydraulic binder foam(i.e. having a viscosity range compatible with the viscosities requiredfor setting the slurry in the annulus) for cementing oil wells or otherwells, with higher mechanical strengths and a lower permeability. Thepresent invention therefore describes the way to formulate a low-densitycementing material by introducing gas in form of bubbles that will beseparated by a very compact cement matrix. In this case, although thematerial obtained is very porous, the permeability of this materialremains very low because the invention described allows to obtain afoamed cement wherein the bubbles are not interconnected.

There are cement formulations with much better mechanical properties, asdescribed for example in document EP-950,034. These formulations arebased on maximization of the packing volume fraction by optimization ofthe grain size of the mineral particles. In fact, it has been known fora long time in the profession (see Féret's formula above) that theproperties of cement materials are improved by increasing thecompactness of the mixture (or, which comes to the same thing, byreducing the porosity). These materials can have compressive strengthsabove 100 MPa and gas permeabilities of the order of one nanoDarcy. Itis well-known that the viscosity of suspensions increases exponentiallywith the volume fraction in solid particles: the significant increase inthe cement slurry viscosity is very serious from an operational point ofview because, in this case, the material can no longer be set in placeby pumping. Now, in the invention described in document EP-950,034,optimization of the grain packing of the mixture of mineral powdersachieved by properly selecting both the size of the mineral particlesand their concentration allows to obtain slurries that are much morefluid than conventional cement slurries. Unlike conventional cements,the high-performance cementing materials described in documentEP-950,034 can have a zero yield point. However, the densities of thesehigh-performance cements as described in document EP-950,034 are above1.9 g·cm⁻³ and they are therefore not suitable for cementing fragile andunconsolidated zones such as those encountered in deep-sea drilling orfor cementing wells in depleted reservoirs. Recently, low-densityformulations, typically ranging between 1.2 and 1.6 g·cm⁻³, weredeveloped for cementing wells drilled in unconsolidated geologic layers.These cementing materials are high-performance materials to which hollowmicrospheres have been added. These materials thus have the samedrawbacks as conventional cements containing hollow microspheres:microsphere crushing during pumping in the well, pozzolanic reactionbetween the portlandite and the silica contained in the microspherewalls. Furthermore, it is impossible to vary the density of the cementduring cementing.

The present invention thus provides a cementing material formulationhaving simultaneously low densities and excellent physical properties,notably compressive strength and permeability. This combination of lowdensities and of improved physical properties in relation to the stateof the art is achieved by foaming cements whose packing volume fractionis maximized by adjusting the proportions of the various grain sizeclasses that make up the material.

SUMMARY OF THE INVENTION

In general terms, the present invention relates to a cementing materialcomprising:

-   -   at least one hydraulic binder from the group consisting of class        G Portland cements, class H Portland cements, aluminous cements        whose alumina content is at least above 30% by mass, and        sulfoaluminous cements,    -   microparticles from the group consisting of microsilica        particles and silico-aluminate particles, whose grain size        ranges between 0.1 and 30 μm, whose proportion ranges between        15% and 50% by mass in relation to the mass of hydraulic binder,    -   mineral particles whose grain size ranges between 1 and 500 μm,        whose proportion ranges between 10% and 35% by mass in relation        to the mass of hydraulic binder, the proportion of particles        being lower than the proportion of microparticles,    -   a hydrosoluble polymer thinning agent whose proportion ranges        between 0.1% and 8% by mass in relation to the mass of hydraulic        binder,    -   water whose proportion is at most 40% by mass in relation to the        mass of hydraulic binder,    -   a foaming agent whose proportion ranges between 0.1% and 10% by        mass in relation to the mass of hydraulic binder.

According to the invention, the material can also comprise a foamstabilizing additive whose proportion ranges between 0.1% and 2% by massin relation to the mass of hydraulic binder, the additive being ahydrosoluble associative polymer comprising hydrophobic units.

The foaming agent can consist of a surfactant compound in a proportionranging between 0.1% and 3% by mass in relation to the mass of hydraulicbinder. The surfactant compound can be selected from among the followingproducts: abietic acid salts, sodium alkyl-aryl sulfonates,phenol-ethoxylates and perfluoroalkyl betaine.

The foaming agent can also be a hydrosoluble polymer referred to as“associative polymer”, comprising hydrophobic chains, the polymer beingin a proportion ranging between 0.1% and 10% by mass in relation to themass of hydraulic binder. The associative polymer can be a polymer withhydrophilic units Hy and hydrophobic units Hb containing C1 to C30alkyl, aryl, alkyl-aryl groups. The associative polymer can have amolecular mass of between 10⁴ and 5×10⁶ daltons and a proportion ofhydrophobic units Hb ranging between 0.5% and 60%.

According to the invention, the mass of microparticles can range between15% and 30% in relation to the mass of hydraulic binder.

The proportion of water can range between 20% and 35% by mass inrelation to the mass of hydraulic binder.

According to the invention, the hydrosoluble polymer thinning agent canbe selected from among the group consisting of: a polynaphthalenesulfonate, a polycarboxylate and a polyoxyethylene polycarboxylate.

The cementing material according to the invention can also comprise aretarding agent for controlling the setting time of the slurry.

The cementing material according to the invention can further comprisean accelerating agent for controlling the setting time of the slurry.

The cementing material according to the invention can be used forcementing an oil well.

The invention also relates to a method of producing a foamed cementslurry wherein the following stages are carried out:

-   -   mixing a powder with water comprising a hydrosoluble polymer        thinning agent so as to obtain a cement slurry, the powder        comprising a hydraulic binder, microparticles and mineral        particles, the hydraulic binder being selected from the group        consisting of class G Portland cements, class H Portland        cements, aluminous cements whose alumina content is at least        above 30% by mass, and sulfoaluminous cements, the        microparticles being selected from the group consisting of        microsilica particles and silico-aluminate particles, of grain        size ranging between 0.1 and 30 μm, whose proportion ranges        between 15% and 50% by mass in relation to the mass of hydraulic        binder, the mineral particles having a grain size ranging        between 1 and 500 μm, with a proportion ranging between 10% and        35% by mass in relation to the mass of hydraulic binder, the        proportion of particles being lower than the proportion of        microparticles, the hydrosoluble polymer thinning agent having a        proportion ranging between 0.1% and 8% by mass in relation to        the mass of hydraulic binder,    -   introducing a foaming agent in the cement slurry, the proportion        of foaming agent ranging between 0.1% and 10% by mass in        relation to the mass of hydraulic binder,    -   pumping the cement slurry comprising the foaming agent, and    -   injecting a gas into the cement slurry comprising the foaming        agent and stirring the mixture of slurry and of gas so as to        foam the slurry and to obtain a foamed cement slurry.

In the method according to the invention, the foaming agent can be asurfactant compound in a proportion ranging between 0.1% and 3% by massin relation to the mass of hydraulic binder. The surfactant can beintroduced in powder form in the cement slurry. The foaming agent canalso be a hydrosoluble associative polymer comprising hydrophobicchains, the polymer being in a proportion ranging between 0.1% and 10%by mass in relation to the mass of hydraulic binder.

In the present invention, the cement material of the walls separatingthe foam bubbles thus has a higher compactness than the materialscommonly used in the profession. The porosity of the cement pastes ofthese new materials was measured by means of a mercury-pump porosimeterand it is below 12%, whereas the porosity of the cement pastes ofconventional foamed cements is above 25%.

The walls between the bubbles of the cement foam described in theinvention being less porous (or more compact, which is equivalent), thepermeability and the mechanical strengths are therefore higher thanthose of the foamed cements obtained from a conventional cement slurry,whose water content is above 40% by weight of cement.

High-performance cements being very fluid, it is difficult to obtain,from these slurries, a stable foam, i.e. whose bubbles do not coalesce.If the bubbles coalesce before the cement hardens, the hardened materialwill be very permeable and have little mechanical strength. Adjustmentof the proportions of the various aggregates that make up the cementslurry according to the invention allows to obtain a stable cement foam,despite the high fluidity of the cementing material. The inventiondescribed in this patent allows to obtain stable high-performance cementfoams and therefore, in fine, a hardened material of very lowpermeability and thus of improved durability.

Furthermore, the setting time of the formulations developed in thepresent invention is shorter than the setting time of a conventionalfoamed cement. In fact, it is known to the man skilled in the art thatthe setting time decreases when the water/cement ratio decreases. Thus,the formulations developed within the scope of the present invention canbe preferred to conventional foamed cements when the temperatures of thewells are low.

Thus, the foamed cement formulations according to the present inventionallow to carry out all the cementing operations required in the case ofwells drilled in low-cohesion formations. The formulations of thepresent invention can also be used for cementing cavernous, fault zonesand more generally zones where fluid losses occur during drilling.

BRIEF DESCRIPTION OF THE FIGURES

Other features and advantages of the invention will be clear fromreading the description hereafter, with reference to the accompanyingfigures wherein:

FIGS. 1 and 2 are photographs of a foamed cement with a foam stabilityproblem,

FIG. 3 is a photograph of a stable foamed cement obtained according tothe invention,

FIG. 4 diagrammatically shows a method of producing a foamed cementslurry according to the invention.

DETAILED DESCRIPTION

According to the invention, the low density and the excellent physicalproperties (compressive strength and permeability) of the cementingmaterial formulations are optimized by combining the followingconstituents:

-   -   a hydraulic binder from the group consisting of the Portland        cements and other hydraulic binders, for example of aluminous        cement type, whose alumina content is above 30%, or        sulfoaluminous cement, or plaster,    -   a microsilica (also referred to as silica fume) of grain size        ranging between 0.1 μm and 30 μm (the BET surface area can range        between 10 and 30 m²/g, preferably 18 m²/g), whose proportion in        the composition according to the invention ranges between 15%        and 50% by mass in relation to the mass of hydraulic binder. In        the invention, the microsilica can be replaced by fly ash        (silico-aluminous, sulfocalcic or silico-calcic particles),    -   a mineral addition of grain size ranging between 1 μm and 500 μm        (which corresponds to a D50 ranging between 35 μm and 210 μm, or        to a specific surface ranging between 0.03 m²/g and 0.65 m²/g).        The amount of mineral added ranges between 10% and 35% by mass        in relation to the mass of hydraulic binder. The proportion of        mineral added remains lower than the proportion of microsilica        so as to respect optimization of the compactness of the packing        of the various aggregates,    -   a superplasticizing agent, also referred to as hydrosoluble        thinning agent, in a proportion ranging between 0.1% and 8% by        mass in relation to the mass of hydraulic binder. The thinning        agent can be either a polynaphthalene sulfonate or a        polycarboxylate, or a polyoxyethylene polycarboxylate,    -   water in a proportion of at most 40% by mass in relation to the        mass of hydraulic binder. It more particularly ranges between        15% and 40%, preferably between 20% and 35%,    -   a foaming agent whose concentration ranges between 0.1% and 10%        by mass in relation to the mass of hydraulic binder. This        foaming agent can be an anionic surfactant (such as sodium        dodecyl sulfate) or a non-ionic surfactant, or a hydrosoluble        polymer comprising hydrophobic links (referred to as associative        polymers), or an air-entraining product, or a mixture of these        molecules, and    -   possibly a foam stabilizing additive. This additive can be a        hydrophobic modified hydrosoluble polymer.

The Portland cements can be Black Label, HTS or CEMOIL cementmanufactured by the Dyckerhoff, Lafarge and CCB Companies respectively.The aluminous cements can be the Secar 51 or Temal cements manufacturedby the Lafarge Aluminates Company.

When the foaming agent is a surfactant compound, it can be in aproportion ranging between 0.1% and 3% by mass in relation to the massof hydraulic binder. The surfactants used in the cement slurryformulation according to the invention can be fatty alcohol sulfatesalso referred to as alkylsulfates of general formula R—O—SO₃X where Xcan be a sodium, ammonium or alkylolamine salt and R a hydrocarbon chaincomprising a number of carbon atoms ranging between 8 and 20. Anothersurfactant class can be the one corresponding to the alkylethersulfates,which comprise between 1 and 10 groups of ethylene oxide. The generalformula of these products is R—O—(CH₂CH₂O)_(n)—SO₃X where n rangesbetween 1 and 10 and R is a hydrocarbon chain comprising a number ofcarbon atoms ranging between 8 and 20. The surfactants of generalformula R—(C₆H₆)—O—(CH₂—CH₂O)_(n)—SO₃X where n ranges between 3 and 15and R is a hydrocarbon chain comprising a number of carbon atoms rangingbetween 8 and 20 can also be used to obtain a cement foam.Phenol-ethoxylates of general formula R—(C₆H₆)—O—(CH₂O)_(n)—HNa where nranges between 3 and 15 and R is a hydrocarbon chain comprising between8 and 18 carbon atoms can be used as foaming agent. Similarly, a cementfoam can be obtained using sodium sulfonate alkyl-aryl surfactants ofgeneral formula R—(C₆H₆)—SO₃Na where R is a hydrocarbon chain comprisingbetween 8 and 18 carbon atoms. Non-ionic surfactants of general formulaR—(COO)—(CH₂CH₂)—(CH₂—CH₂—O)_(n)—H where n ranges between 1 and 24, aswell as non-ionic surfactants whose hydrophobic part is a hydrocarbonchain of formula CH₃(CH₂)_(m) and whose hydrophilic part is anoxyethylene chain of formula (CH₂CH₂O)_(n) where m ranges between 8 and20 and n ranges between 2 and 24 can also be used in the invention. Thehydrophilic groups can also be sugars or glycerol derivatives. Thesetypes of surfactant, notably alkylpolyglucosides, have a higherefficiency in the formation of foams and their use is advantageous inhighly salted media such as cement slurries. Furthermore, thesesurfactants have a very good biodegradability. Cationic surfactants canbe used, notably alkylamine salts of general formula:

where R is a hydrocarbon chain consisting of 8 to 20 carbon atoms, R′,R″ and R′″ correspond to hydrogen atoms or methyl, ethyl, benzyl oroxyethylene groups, and X an anion.

The foaming agent can also be abietic acid salt of general formulaC₂₀H₃₀O₂—X, where X is a sodium, potassium salt.

Advantageously, zwiterrionic surfactants can be used, for example alkylamidobetaine of general formula C_(n)H_(2n+1)CONH(CH₂)₃N⁺(CH₃)₂CH₂COO⁻where n ranges between 10 and 18. It is also possible to use thefluorinated form of this surfactant. Perfluoroalkyl betaine gives goodquality and stable foams. Perfluorobetaine also affords the advantage ofbeing chemically stable at high temperatures.

A mixture of these surfactants can be advantageously used. This mixturecan also comprise cosurfactants. These cosurfactants can be fattyalcohols.

When the foaming agent is an associative polymer, it can be in aproportion ranging between 0.1% and 10% by mass in relation to the massof hydraulic binder.

The associative polymers used in the composition of the cement slurryaccording to the invention can be a polymer with hydrophilic (Hy) andhydrophobic (Hb) units in aqueous solution, the hydrophobic units (Hb)containing C1 to C30 alkyl, aryl, alkyl-aryl groups, the polymer havingthe following structure -(Hb)-(Hy)- with a statistical distributionwith:

-   -   Hy of the form:        where R5 is H or CH₃, Z1 is COOH or CONH₂ or CONHR1SO³⁻ or        CONHR″1, R″1 is CH₃,    -   or of the form:        where R5 is H or CH₃, Z1 is CONH₂ or CONHR″1, R″1 is CH₃ and R″5        is H or CH₃, Z3 is COOH or CONHR1SO³⁻, and where R1 is C₃H₈ or        C₆H₅,    -   Hb is of the form:        where R′5 is H or CH₃ and Z2 is COOR7, COOR′1, CONR1R′1 or        CONR1R7, R7 being a non-ionic surfactant consisting of an alkyl        polyoxyethylene chain, R1 is H or a C1-C30 alkyl, aryl or        alkyl-aryl radical, and R′1 is a C₁-C₃₀ alkyl, aryl or        alkyl-aryl radical.

In particular, the polymer can have a molecular mass of between 10⁴ and5×10⁶ daltons, more precisely between 10⁴ and 1.5×10⁶, and a proportionof hydrophobic units Hb ranging between 0.5 and 60%.

According to the present invention, the associative polymer can also bea derivative of the hydrophilically and hydrophobically modifiedgalactomanane described in patent U.S. Pat. No. 4,960,876. Thisassociative polymer is produced by the Lamberti Company and marketedunder references HPG19, HPG21, HM21, HM22. The molecular mass of themodified galactomanane can be below 5×10⁶ daltons, preferably below2×10⁶ daltons. The hydrophobic group can be a linear or branched alkylradical, saturated or with an ethylene unsaturation, comprising between10 and 32 carbon atoms, preferably between 12 and 30. Adding to thecement slurry a proportion of hydrophilically and hydrophobicallymodified galactomanane derivative or a proportion of a mixture ofhydrophobically modified hydrosoluble polymers as described above and ofhydrophilically and hydrophobically modified galactomanane derivativesallows to obtain cement foams of different densities, lower than theinitial density of the cement slurry.

The associative polymer can be selected from the group consisting of:

-   -   HMPAM1: where R5 is H and Z1 is CONH₂, R′5=CH₃, Z2 is COOR′1        with R′1=C₉H₁₉,    -   HMPAM2: where R5 is H and Z1 is CONH₂, R′5=H, Z2 is CONR′1R′1        with R′1=C₆H₁₃,    -   HMPAM3: where R5 is H and Z1 is CONH2, R″5=H, Z3 is COOH or        CONHR1SO₃, where R1 is C₃H₈ (AMPS), R′5=H, Z2 is CONR′1R′1 with        R′1=C₆H₁₃,    -   S1: where R5 is H and Z1 is CONH₂, R′5=H and Z2 is C₆H₄ SO₃H,    -   HB1: where R5 is H, Z1 is COOH, R′5 is H and Z2 is COOR′1 with        R′1=C₄H₉.

In particular, the polymer called HMPAM1 or HMPAM2 or HMPAM3 can have amolecular mass of between 5×10⁵ daltons and 2×10⁶ daltons, and aproportion of hydrophobic units (Hb) ranging between 0.5 and 3%.

Polymer S1, an acrylamide (Hy)/styrene sulfonate (Hb) copolymer,branched or not, according to the description above can have a molarratio of about 50/50 and a molar mass ranging between 5×10⁵ daltons5×10⁶ daltons. If it is branched, it is referred to as S2. The branchingagent used in this case can be N,N′ methylene bis acrylamide MBA.

Polymer HB1, an acrylate (Hy)/butyl acrylate (Hb) copolymer, with R5being H, Z1 COOH, R′5H and Z2 COOR′1 with R′1 C4, can comprise between50% and 80% acrylate units, and have a molecular mass of between 10⁴ and5×10⁶ daltons, preferably between 10⁴ and 5×10⁴ daltons.

In order to obtain a cement slurry as stable as possible, proportions ofthe various constituents of the cement slurry can be selected from thefollowing range:

-   -   20 g to 50 g microsilica or fly ash to 100 g hydraulic binder,        the microsilica preferably having a specific surface ranging        between 10 and 30 m²/g,    -   10 g to 35 g mineral addition to 100 g hydraulic binder, the        mineral addition preferably having a D50 ranging between 35 and        210 μm, for example between 35 and 90 μm or between 140 and 210        μm.

When a surfactant is added to a slurry conventionally used in theprofession (which behaves like a Bingham fluid) and stirred so as toentrain air within, the presence of the yield point prevents migrationof the air bubbles created. Migration of the air bubbles can lead eitherto a non-foamed slurry when the air bubbles migrate to the surface, orto a very weakly foamed slurry (with a higher density than thatexpected), or to a foamed or very little foamed slurry but with agreatly connected foam structure (due to the coalescence of the airbubbles). The presence of a yield point in the slurry to be foamed is anadvantage when it is desired to obtain high-quality foamed cements. Inthe case of cement slurries comprising various grain sizes, there is notnecessarily a yield point: the slurry has a Newtonian type behaviour. Itis then difficult to maintain the air bubbles evenly distributed in thevolume. To obtain a stable and homogeneous foam with these very fluidslurries, there are several solutions. Viscosifiers such as those knownand used in the profession can for example be added. It is also possibleto add to the very fluid cement slurry formulation associative polymersin proportions ranging between 0.1% and 2.0%, and preferably between0.1% and 1.0%. Another way to obtain stable foams from very fluidslurries (i.e. having a very low yield point or with a Newtonianbehaviour) consists in preparing the cement slurry, then in adding thesurfactant in powder form just before stirring. It has been observed inthe laboratory that with this method the foams obtained were more stablethan when the surfactant was added in liquid form. To obtain homogeneousfoamed cements with different densities, the stirring time has to beoptimized. The stirring time depends on the type of slurry, on the typeof surfactant used and possibly on the presence of a viscosifier: eachcase requires optimization of the stirring time (stirring is understoodto be entrainment of air in the slurry). For example, above a certainstirring time, it has been observed in the laboratory that the densityno longer decreases. It has also been noticed that too long a stirringtime could eventually break the cement foam. Producing a foamed cementfrom a cement slurry more fluid (fluid means that the yield point is lowor non-existent, like the cement slurries involving different grainsizes, such as the cement slurry according to the invention) than thosegenerally used in the profession is not a trivial operation.

The cement slurry comprising different grain sizes is very fluid and,according to circumstances, there may be an absence of yield point, i.e.the cement flows only under the effect of the gravity force. Thisfluidity can be the cause for a lack of stability of the cement foam. Anassociative polymer can be added to improve the foam stability, in aproportion ranging between 0.1% and 2%, preferably between 0.1% and 1%.This associative polymer allows to increase the viscosity of the slurry,which has the effect of limiting coalescence of the gas bubbles.

When the foaming agent is an associative polymer, the cement formulationdoes not necessarily require a foam stabilizing additive. In fact,certain associative polymers, for example HB1, simultaneously allow tofoam the cement slurry and to stabilize the foam.

Furthermore, the formulation of the cementing material according to theinvention can comprise a retarding agent allowing to retard the settingtime of the cement slurry.

The retarding agents can be organic products or water-soluble mineralmaterials.

Among the organic products, the following molecules can bedistinguished:

-   -   (calcium, sodium) lignosulfonates whose sugar proportions are        below 20%,    -   acids and salts (sodium, potassium, calcium) of        hydroxycarboxylic acids,    -   oxalic and gluconic acids, efficient with very low dosages,    -   sodium gluconate of formula CH₂OH(CHOH)₄COONa is very active for        retarding materials containing hydraulic binders,    -   calcium gluconate,    -   carbon hydrates of general formula C_(n)(H₂O)_(n); among these        molecules, the saccharose of formula C₁₂H₂₂O₁₁ is very        efficient; it is also possible to use glucoses (C₆H₁₂O₆), starch        (C₆H₁₂O₆)_(n), and cellulose,    -   corn syrup.

These organic products can be used in dosages ranging between 0.1% and5% by mass of dry extract in relation to the mass of hydraulic binder.

Among the retarding agents based on mineral salts, the followingproducts can be used:

-   -   boron compounds used with very low dosages can be used to retard        the cementing materials; boric acid (BO₃H₃), borax        (Na₂B₄O₇₁₀H₂O), sodium metaborate Na₂B₂O₄ and sodium tetraborate        (Na₂B₄O₇) can be preferably used,    -   tin sulfate (S₂SO₄),    -   lead acetate (Pb(C₂H₃O₂)₂),    -   calcium monophosphate (Ca(H₂PO₄)₂).

These retarding agents based on mineral salts can be used with dosagesranging between 0.1% and 2% by mass in relation to the mass of hydraulicbinder.

Furthermore, the formulation of the cementing material according to theinvention can comprise an accelerating agent allowing to accelerate thesetting time of the cement slurry. This accelerating agent can be usedfor cementing zones with low temperatures between −4° C. and 10° C. Forexample, the zones close to the sea bottom in deep-sea drilling can beat temperatures of about 4° C.

The accelerating agents can be selected from among the followingproducts:

-   -   calcium chloride (CaCl₂),    -   calcium nitrite (Ca(NO₂)₂),    -   calcium formiate (Ca(HCO₂)₂).

These products can be used at concentrations ranging between 0.5% and 5%by mass in relation to the mass of hydraulic binder. For temperaturesbelow 15° C., calcium chloride should not be used at concentrationsabove 2.5% in relation to the mass of cement. Above this concentration,it behaves like a setting retarding agent under low-temperatureconditions.

Non-chlorinated accelerating agents available on the market can also beused.

Depending on the proportion of the various constituents mentioned above,the foamed cement obtained may not be stable as shown in FIGS. 1 and 2.In fact, depending on the proportion of the various constituents, theslurry may have a segregation.

In this type of formulation, a considerable drainage occurs before thecement hardens. In FIG. 1, a two-phase system has formed with a cementslurry in lower part 1 and a very aerated and connected foam in upperpart 2. FIG. 2 shows an enlargement of part 2 of FIG. 1. Such a foamedcement formulation is not satisfactory for well cementing. According tothe invention, the proportion of the different constituents has beenoptimized to obtain a stable and homogeneous foamed cement with improvedproperties. Obtaining stable foamed cements with improved propertiesnotably requires optimizing the grain packing and the amount of foamingagents.

FIG. 3 shows the foamed cement structure obtained according to thepresent invention: it can be clearly seen that the bubbles have notcoalesced. The bubbles are separate and independent.

The following cement slurry formulations allow to illustrate theinvention.

The influence of the foaming agent concentration was evaluated for aslurry comprising: a water/cement ratio E/C=0.27; microsilica=24%;mineral addition=20%. Anionic surfactant concentration (g/100 g cement)0.25 0.40 0.75 Density (g/cm³) 1.70 1.32 1.24 Rc (MPa) 32 17 12.5

The influence of the foaming agent concentration was evaluated for aslurry comprising: a water/cement ratio E/C=0.27; microsilica=50%;mineral addition=20%. Anionic surfactant concentration (g/100 g cement)0 0.25 0.5 0.75 Density (g/cm³) 2.25 2.03 1.74 1.63 Rc (MPa) 123 74 4039

The influence of the foaming microsilica content was evaluated for aslurry comprising: a water/cement ratio E/C=0.27; mineral addition=20%,foaming agent (surfactant) concentration=0.75%. Microsilica content(g/100 g cement) 24 30 50 Density (g/cm³) 1.24 1.42 1.63 Rc (MPa) 12.519 39

By varying the amount of foaming agent between 0 and 0.75%, it isobserved that it is possible to lower the density of the material from2.25 to 1.24 g/cm³.

When an identical amount of foaming agent (0.75% for example) is added,it is observed that lower densities are obtained when the amount ofmicrosilica is small. Foamed cements of lower densities are obtained byselecting formulations comprising microsilica amounts ranging between15% and 30% by mass in relation to the mass of hydraulic binder.

Finally, it can be noted that the formulations with 50% microsilicaafford a very high compressive strength Rc. Thus, for a formulation ofdensity 1.63 g/cm³ containing 50% microsilica and prepared according tothe invention, the compressive strength is 39 MPa, which is above thevalue measured for a non-foamed cement paste of density 1.9 g/cm³. Thecementing materials obtained according to the invention thus allow toreach low densities without losing their mechanical strength however.

Two cement slurries of equivalent density are compared: a conventionalfoamed cement and a high-performance foamed cement according to theinvention.

Conventional Foamed Cement Formulation:

-   -   Class G Portland cement: 100    -   Water/Cement: 44%    -   Sodium Dodecyl Sulfate/Cement: 4.4×10⁻²%.

High-Performance Foamed Cement Formulation According to the Invention:

-   -   Class G Portland cement: 100    -   Water/Cement: 27%    -   Microsilica: 24%    -   Mineral addition: 20%    -   Sodium Dodecyl Sulfate/Cement: 0.625%.

The following table allows to compare the properties of the twomaterials: Conventional High-performance Measured quantities foamedcement foamed cement Density (g cm⁻³) 1.32 1.30 Compressive strength(MPa) 6.8 18.4 Bending strength (MPa) 2.7 3.9 Young's modulus (GPa)4.302 7.394 Gas permeability (m²) 3.9 × 10⁻¹⁶ 7.8 × 10⁻¹⁷

From the values obtained for the two materials, it is clear that thehigh-performance foamed cement according to the invention has betterproperties than a conventional foamed cement as regards its mechanicalstrength and permeability.

It is very interesting to note that the permeability obtained for thehigh-performance foamed cement is equivalent to that of a non-lightenedcement (of water/cement ratio 0.44) conventionally used for cementingcasings in oil wells. In fact, the permeability of such a cement is8×10⁻¹⁷ m². Thus, although the material which is the object of thepresent invention has a markedly higher porosity (of the order of 50%)than a conventional cement, its permeability is equivalent, which is anadvantage notably in terms of durability.

FIG. 4 diagrammatically shows a method of producing a foamed cementslurry according to the invention.

Mixer 7 allows to mix a powder comprising a hydraulic binder withmicroparticles and mineral particles added, as described above, comingfrom tank 1 through line 5, with water coming from tank 2 through line6. The water contains thinning agents. Valves 3 and 4 allow to controland to adjust the amounts of water and of the powder mixture containingthe hydraulic binder introduced in mixer 7. A homogeneous cement slurryis obtained at the outlet of mixer 7 and flows through line 8.

Tank 9 contains foaming agents: surfactants or hydrosoluble polymerscomprising hydrophobic links. Foaming agents are injected by means ofpump 10, valve 11 and line 12 into the cement slurry circulating in line8. The surfactants can be introduced in the slurry in powder form justat the mixer outlet.

The cement slurry comprising foaming agents is pumped by slurry pump 13until a high pressure ranging for example between 10 and 100 bars isreached.

A gas is then injected into the slurry at high pressure through line 14.The gas can be air or nitrogen. Injection of air into the cement slurryis achieved in foam generator 15 whose function is to stir the slurryand the gas so as to foam the cement slurry. Foam generator 15 cancreate turbulences in the slurry in different ways known to the manskilled in the art. A foamed cement slurry is obtained at the outlet offoam generator 15 and discharged through line 16.

The foamed cement slurry is either sent into a tank through line 17 orintroduced into a well to be cemented through line 18.

Densimeters 19, 20 and pressure detectors 21, 22 allow to control thedensity and the pressure of the slurry prior to and after foaming.

1) A cementing material comprising: at least one hydraulic binder fromthe group consisting of class G Portland cements, class H Portlandcements, aluminous cements whose alumina content is at least above 30%by mass, and sulfoaluminous cements, microparticles from the groupconsisting of microsilica particles and silico-aluminate particles,whose grain size ranges between 0.1 and 30 μm, whose proportion rangesbetween 15% and 50% by mass in relation to the mass of hydraulic binder,mineral particles whose grain size ranges between 1 and 500 μm, whoseproportion ranges between 10% and 35% by mass in relation to the mass ofhydraulic binder, the proportion of particles being lower than theproportion of microparticles, a hydrosoluble polymer thinning agentwhose proportion ranges between 0.1% and 8% by mass in relation to themass of hydraulic binder, water whose proportion is at most 40% by massin relation to the mass of hydraulic binder, a foaming agent whoseproportion ranges between 0.1% and 10% by mass in relation to the massof hydraulic binder. 2) A material as claimed in claim 1, furthercomprising a foam stabilizing additive whose proportion ranges between0.1% and 2% by mass in relation to the mass of hydraulic binder, theadditive being a hydrosoluble associative polymer comprising hydrophobicunits. 3) A material as claimed in claim 1, wherein the foaming agent isa surfactant compound in a proportion ranging between 0.1% and 3% bymass in relation to the mass of hydraulic binder. 4) A material asclaimed in claim 3, wherein the surfactant compound is selected fromamong the following products: abietic acid salts, sodium alkyl-arylsulfonates, phenol-ethoxylates and perfluoroalkyl betaine. 5) A materialas claimed in claim 1, wherein the foaming agent is a hydrosolubleassociative polymer comprising hydrophobic chains, the polymer being ina proportion ranging between 0.1% and 10% by mass in relation to themass of hydraulic binder. 6) A material as claimed in claim 1, whereinthe associative polymer is a polymer with hydrophilic units Hy andhydrophobic units Hb containing C1 to C30 alkyl, aryl, alkyl-arylgroups. 7) A material as claimed in claim 6, wherein the associativepolymer has a molecular mass of between 10⁴ and 5×10⁶ daltons and aproportion of hydrophobic units Hb ranging between 0.5% and 60%. 8) Amaterial as claimed in claim 1, wherein the mass of microparticlesranges between 15% and 30% in relation to the mass of hydraulic binder.9) A material as claimed in claim 1, wherein the proportion of waterranges between 20% and 35% by mass in relation to the mass of hydraulicbinder. 10) A material as claimed in claim 1, wherein the hydrosolublepolymer thinning agent is selected from among the group consisting of: apolynaphthalene sulfonate, a polycarboxylate and a polyoxyethylenepoly-carboxylate. 11) A material as claimed in claim 1, furthercomprising a retarding agent for controlling the setting time of theslurry. 12) A material as claimed in claim 1, further comprising anaccelerating agent for controlling the setting time of the slurry. 13) Amaterial as claimed in claim 1, used for cementing an oil well. 14) Amethod of producing a foamed cement slurry, wherein the following stagesare carried out: mixing a powder with water comprising a hydrosolublepolymer thinning agent so as to obtain a cement slurry, the powdercomprising a hydraulic binder, microparticles and mineral particles, thehydraulic binder being selected from the group consisting of class GPortland cements, class H Portland cements, aluminous cements whosealumina content is at least above 30% by mass, and sulfoaluminouscements, the microparticles being selected from the group consisting ofmicrosilica particles and silico-aluminate particles, of grain sizeranging between 0.1 and 30 μm, whose proportion ranges between 15% and50% by mass in relation to the mass of hydraulic binder, the mineralparticles having a grain size ranging between 1 and 500 μm, with aproportion ranging between 10% and 35% by mass in relation to the massof hydraulic binder, the proportion of particles being lower than theproportion of microparticles, the hydrosoluble polymer thinning agenthaving a proportion ranging between 0.1% and 8% by mass in relation tothe mass of hydraulic binder, introducing a foaming agent in the cementslurry, the proportion of foaming agent ranging between 0.1% and 10% bymass in relation to the mass of hydraulic binder, pumping the cementslurry comprising the foaming agent, and injecting a gas into the cementslurry comprising the foaming agent and stirring the mixture of slurryand of gas so as to foam the slurry and to obtain a foamed cementslurry. 15) A method as claimed in claim 14, wherein the foaming agentis a surfactant compound in a proportion ranging between 0.1% and 3% bymass in relation to the mass of hydraulic binder. 16) A method asclaimed in claim 15, wherein the surfactant is introduced in powder forminto the cement slurry. 17) A method as claimed in claim 16, wherein thefoaming agent is a hydrosoluble associative polymer comprisinghydrophobic chains, the polymer being in a proportion ranging between0.1% and 10% by mass in relation to the mass of hydraulic binder.